Detergent composition



United States Patent 3,011,977 DETERGENT COMPOSITION Bernhard Raecke, Dusseldorf, Germany, assignor to Henkel & Cie., G.m.b.H., Dusseldorf-Holtlrausen, Germany, a corporation No Drawing. Filed July 23, 1956, Ser. No. 599,326

11 Claims. (Cl. 252-161) This invention relates to a detergent composition, and more particularly relates to a synthetic detergent composition which will not form precipitates or curd in hard water, and which will not irritate the skin.

Synthetic detergent compositions are well known and widely used for general household and laundry purposes. Besides, their excellent cleaning characteristics, the synthetic detergents, have the advantage over soaps in that they are not affected by hard water, since their alkaline earths and light-metal salts are soluble in water.

The synthetic detergents, however, have the disadvantage that the same tend to irritate the skin, causing it to becomered, brittle, and chapped. For this reason the synthetic detergents are preferably used by housewives in automatic machines and where the same do not have to come into direct contact with the skin. The exact cause of the skin irritation is not known, but presumably is caused by the strong emulsifying action of the detergent, which removes too much fat and oil from the skin.

The commercially available synthetic detergents generally contain, as the synthetic detergent ingredient, watersoluble alkyl and alkyl aryl sulfonates and sulfates containing 21 higher alkyl radical with not less than about 8 and not more than about 20 carbon atoms.

. In addition to the sulfonates and sulfates, the detergent compositions, particularly when the same are intended for laundry purposes, as, for example, in the washing of white linens, also contain. alkaline reacting materials, such as soda, phosphates, pyro-, polyand metaphosphates, borax, waterglass, and the like.

. tion:

It has now been found that the skin irritation caused by the synthetic detergents can be eliminated or substantially reduced by the addition of complex aluminum compounds which are soluble in aqueous solutions of the detergent.

Any water-soluble complex aluminum compound formed by an addition with an aluminum salt may be used, but ordinary aluminum salts, as, for example, aluminum sulfate or aluminates, which form insoluble gels of aluminum hydroxide in the washing solution are unsatisfactory and will not have any effect on the irritating action of the detergent.

For the formation of the water-soluble complex aluminum compounds there are preferably used hydroxy carboxylic acids or polycarboxylic acids, such as tartaric acid, citric acid, malic acid, glycolic acid, or lactic acid. These complex-forming acids may be used either in their free form or in the form of their salts, and preferably their sodium, potassium, or ammonium salts. It is also possible to use mixed acids or mixed salts, as, for example, sodium potassium tartrate or sodium ammonium citrate. It has been found most preferable to use citric acid, tartaric acid, and/or their salts as the complexforming acids.

Any water-soluble aluminum salt of an organic or inorganic acid may be used to form the water-soluble compie x aluminum compounds. The customary commercially available salts, such as alum, aluminum sulfate, alumi- "-'num acetate, or aluminum chloride are preferably used for this purpose, though other water-soluble aluminum salts may also be employed, as, for example, aluminum nitrate.

The amount of the complex aluminum compounds added is not critical, and even small percentages are sufficient to result in a noticeable improvement of the skinprotecting properties. It is also possible to use larger quantities Without any detrimental effect.

It has been found advantageous to add amounts of the complex aluminum compound of about 1 to 20% by weight, and preferably 3 to 10% by weight to the detergent composition.

The addition may be effected in any desired manner, as, for example, by mixing the components with each other in ordinary mixers or homogenizers, such as edge mills. It is also possible to use the well-known spray methods for combining the ingredients.

The complex aluminum compounds show the beneficial protective action against skin irritation with any compositions containing a synthetic detergent which will not form a curd or precipitate in hard Water. The detergent compositions may preferably additionally contain any of the conventional alkaline detergent additives, such as the various phosphates, borax, waterglass, and the like.

The synthetic detergent ingredients of the composition in accordance with the invention include any of the watersoluble, alkali metal salts of organic reaction products having a higher molecular alkyl radical of about 8 to 20 carbon atoms, such as the sulfates and sulfonates. These include the well-known water-soluble salts of high-molecular, aliphatic sulfuric acid esters, such as the alkali metal salts of sulfuric acid esters of normal, primary, aliphatic alcohols having 12 to 18 carbon atoms, particularly those whose principal active ingredient is a watersoluble salt of lauryl sulfuric acid or oleyl sulfuric acid.

Examples of these sulfates include the sodium alkyl sulfate obtained from the mixed higher alcohols produced by the reduction of tallow, coconut oil, palm kernel oil, or other oils of the coconut oil group, or the sodium alkyl sulfate derived from the higher alcohols of sperm oil. 1

In addition to the alkyl sulfates mentioned above,

.water-soluble salts of other aliphatic sulfuric acids may be used, as, for example, water-soluble salts of sulfuric acid esters of higher fatty acid monoglycerides, such as the sodium salt of coconut oil fatty acid mono-ester. of 1,2-dihydroxy-propane-3-sulfuric acid ester and of the sulfated higher fatty acid alkanol emides, such as the sodium salt of sulfated coconut oil fatty acid ethanol amide. Sulfonates which may be used include watersoluble salts of higher monofatty acid esters 1,2-dihydr0xy-propane-3-sulfonic acid, which is the sodium salt of the coconut oil fatty acid mono-ester of this sulfonic acid. Additionally, water-soluble salts of higher fatty acid mono-esters of lower-molecular weight hydroxy alkyl sulfonic acid, such as oleic acid ester of the sodium salt of isethionic acid and of the higher fatty acid amide of lower-molecular amiclo alkyl sulfonic acids, such as the ammonium salt of oleic acid amide N-metal taurine, may be used. Water-soluble salts of the higher alcohol esters of sulfocarboxylic acids, such as .the sodium salt of lauryl alcohol ester of sulfoace-tic acid, higher alkylated benzene sulfonic acids, such as the potassium salt of the sulfonic acid derived from the condensation product of 3-sodium sulfonate may also be used.

In addition to the above noted materials, surfaceaactive agents of an anionic or non-ionic nature may be used 100" c. v product, which forms a clear solution in water.

. I 3 as the detergent component. The non-ionic surface-active agents include, for example, the addition products of ethylene oxide or propylene oxide to fatty acids, fatty acid alcohols, fatty acid amides, etc.

This group is merely representative of the various hardwater synthetic detergents which may be present in the composition in accordance with the invention and any of the materials commonly designated as a hard-Waterresistant synthetic detergent may be used. These detergents are resistant to lime, magnesia, and similar compounds contained in hard water.

As the alkyl benzene sulfonates and alkyl sulfonates are among the more commonly used synthetic detergents which are irritating to the skin, the composition in accordance with the invention containing the Water-soluble, complex aluminum compounds, and'these sulfonates and sulfates are preferable in accordance with the invention.

Other synthetic detergents which are preferably used include Water-salts of parafiin sulfonic acids, such as sodium kerosene'sulfonates having an alkyl group with about 12 carbon atoms, fatty alcohol sulfates, such as the watersoluble potassium alkyl sulfate, having an alkyl group derived from normal primary aliphatic alcohols with 8 to 18 carbon atoms, salts of alkylated benzene and naphithalene sulfonic acids, such as the sodium salts of these acids with an alkyl group derived from the condensation product of benzene and polypropylenes having 9 to 15 carbon atoms and averaging about 12 carbon atoms, and the saltsoffatty acid condensation products of taurines, such as are sold commercially under the name of Igepon (sodium-N-methyl-N-oleyl taurate).

The composition may be produced and marketed in any desired form, as, for example, conventional powder,

granular flake, or even in the form of solutions.

Due to the mild action of the composition on the skin,

:the same may be conveniently produced and marketed in the form of soap bars or pieces for general hand use.

The following examples are given to further illustrate the invention, but not to limit the same:

Example 1 300 parts by weight crystalline aluminum sulfate are dissolved in 750 parts by weight of water. A solution of a 300 parts by weight Seignettes salt (K-Natartrate) in 750 parts by weight of Water is added and the entire solution is brought to a pH of 7 7.5 by means of concentrated caustic soda solution. The solution obtained in this manner is sprayed in an atomization tower with hot air of 95- There is obtained a white, aluminum-containing A cleansing agent for laundry is prepared with this product in the following manner: 13 parts by weight of sodium alkyl benzene sulfonate (the alkyl group in the alkylbenzenesulfate used has an average chain length of G i-I 20 parts by weight of a potassium fatty alcohol sulfonate with the alkyl group derived from normal primary aliphatic alcohols having 10 to 18 carbons, parts by weight sodium paraffin sulfonate having an alkyl group "with about 12 carbon atoms (trade name Mersolat),

30 parts by weight soda, 12 parts by weight tetrasodium pyropho'sphate, 20 parts by weight Glaubers salt and parts by weight of the afore-mentioned aluminum-containing product are mixed well with one another in an ordinary mixer. There is obtained an excellent detergent suitable for laundering, which is not harsh on sensitive hands.

- Example 2 A detergent powder for laundry, which has the following composition is intimately mixed during or after preparation with 7 parts of the aluminum complex mentioned in Example 1:

' 10 parts by weight sodium alkylbenzene sulfonate (alkyl radical of average chain length C 10 parts'by weight sodium salt of coconut fatty alcohol sulfate;

. 4 10 parts by weight of tetrasodium pyrophosphate; 25 parts by weight of sodiumv tripolyphosphate; 5 parts by weight waterglass; 2 parts by weight coconut fatty acid mono-ethanol amide; 1 part by weight carboxyl methyl cellulose; I parts by weight sodium sulfate; 11 parts by weight water.

The detergent powder had the same cleansing action as the powder without the'aluminum complex, but was very gentle to the. hands, whereas the powder without the complex was harsh and irritating.

' Example 3 300 parts by weight crystalline aluminum sulfate (Al (SO .18H O) are dissolved in 750 parts by weight of water. There is then added a solution of 220' parts by weight citric acid in 500 parts by weight of water and the entire solution is brought to a pH of 8 by means of concentrated caustic }soda solution. The solution obtained in this manner is sprayed in the customary manner in a spraying dryer with hot air of to C. There is obtained a white powderwhich forms a clear solution when dissolved in water. 5 parts by weight of this powder are mixed with a dish-washing or fine washing agent of the following composition:

.Instead of adding the aluminum complex compound in ,dry form, a corresponding quantity of the solution of the complex salts can also be. sprayed jointly with the detergent, or dried in some other manner.

The detergent compositon was very gentleto the hands,

,whereas without the aluminum complex, the same was very harsh and irritating.

Example 4 5 parts by weight of the aluminum complex compound described in Example 1 are incorporated in a synthetic cake soap of the following composition:

35 parts by weight sodium salt of coconut fatty alcohol sulfate;

35 parts by weight sodium salt of tallow alcohol sulfate;

5 parts by' weight of coconut fatty acid mono-ethanolamide;

. 10 parts by weight polyglycol ethers of an average molecular weight of 6000; 5 parts by weight fatty alcohol of a chain length C -C 5 parts by weight tripolyphosphate.

The synthetic cake soap thus obtained constitutes an excellent personal soap and does not irritate even sensitive skin.

Example 5 Example 2 was repeated, using, however, in place of the 10 parts by weight of the sodium salt of coconut oil alcohol sulfonate 5 parts by weight of a sodium salt of coconut oil alcohol sulfate and 5 parts by weight of the addition product of 6 mols of ethylene oxide and 1 mol of coconut oil alcohol. The detergent product produced corresponded to the powder produced in Example 2 and was very gentle to the hands in use, whereas the same powder without the complex was harsh and irritating.

In the foregoing examples the coconut fatty acids and alcohols referred to were derived from a coconut oil mixture consisting predominantly of compounds having from 12 to 18 carbon atoms. The tallow alcohol sulfate mentioned is a sulfate which was prepared from an alcohol of a chain length of C C formed from tallow.

In the examples the described detergents may be replaced by any of the detergents mentioned in the foregoing description. In place of the complex aluminum compounds mentioned any of the aluminum complexes formed from hydroxycarboxylic acid or polycarboxylic acid, such as malic acid, glycolic acid, lactic acid, or their salts, and water-soluble aluminum salts, such as alum, aluminum acetate, aluminum chloride or aluminum nitrate, may be used.

' In place of the alkaline materials added, any of the known or conventional, inorganic alkaline detergent additives may be used.

While the invention has been described in detail with reference to the specific embodiment shown, various changes and modifications will become apparent to the skilled artisan, which fall within the spirit of the invention and scope of the appended claims.

I claim:

1. A detergent composition comprising a synthetic capillary active anionic detergent which will not form curd in hard water and from about 120%, by weight of the detergent composition of a complex aluminum compound soluble in an aqueous solution of the detergent composition formed by the reaction of a water-soluble aluminum salt selected from the group consisting of alum, aluminum sulfate, aluminum acetate, aluminum chloride and aluminum nitrate, and a member selected from the group consisting of tartaric acid, citric acid, malic acid, glycolic acid, lactic acid and the sodium, potassium, ammonium and mixed salts of said acids, said aluminum salt and acid group member reacting in the ratio of about 2.3 mols of salt to one mol of the acid group member in the form of their aqueous solutions, whereupon the pH of the resulting solution is adjusted to from neutral to slightly alkaline, and thereafter the aqueous solution is evaporated to dryness.

2. A detergent composition according to claim 1, in which said complex aluminum compound is formed by the reaction of aluminum sulfate and citric acid, whereupon the pH of the resulting solution is adjusted to about 8, and thereafter the aqueous solution is evaporated to dryness.

3. A detergent composition according to claim 1, in which said complex aluminum compound is formed by the reaction of aluminum sulfate and sodium potassium tartrate, whereupon the pH of the resulting solution is adjusted to about 7-7.5, and thereafter the aqueous solution is evaporated to dryness.

4. A detergent composition according to claim 1, additionally containing an inorganic alkaline detergent additive.

5. A detergent composition comprising a detergent selected from the group consisting of sulfonates and sulfates containing higher alkyl radicals of about 820 carbon atoms and from about 1-20% by weight of the detergent composition of a complex aluminum compound soluble in an aqueous solution of said composition formed by the reaction of a water-soluble aluminum salt selected from the group consisting of alum, aluminum sulfate, aluminum acetate, aluminum chloride and aluminum nitrate, and a member selected from the group consisting of tartaric acid, citric acid, malic acid, glycloie acid, lactic acid and the sodium, potassium, ammonium and mixed salts of said acids, said aluminum salt and acid group member reacting in the ratio of about 2.3 mols of salt to one mol of the acid group member in the form of their aqueous solutions, whereupon the pH of the resulting solution is adjusted to from neutral to slightly alkaline, and thereafter the aqueous solution is evaporated to dryness.

6. A detergent composition comprising a water-soluble alkali metal salt of an alkyl aryl sulfonate having an average alkyl chain length of about C and from about 1 to 20% by weight of the detergent composition of a complex aluminum compound soluble in an aqueous solution of said sulfonate formed by the reaction of a water-soluble aluminum salt selected from the group consisting of alum, aluminum sulfate, aluminum acetate, aluminum chloride and aluminum nitrate, and a member selected from the group consisting of tartaric acid, citric acid, malic acid, glycolic acid, lactic acid and the sodium, potassium, ammonium and mixed salts of said acids, said aluminum salt and acid group member reacting in the ratio of about 2.3 mols of salt to one mol of the acid group member in the form of their. aqueous solutions, whereupon the pH of the resulting solution is adjusted to from neutral to slightly alkaline, and thereafter the aqueous solution is evaporated to dryness.

7. A detergent composition according to claim 6, in which said alkyl aryl sulfonate is an alkyl benzene sulfonate having an alkyl group derived from the condensation product of benzene and polypropylene having 9 to 15 carbon atoms and averaging about 12 carbon atoms.

8. A detergent composition comprising a water-soluble alkali metal alkyl sulfate having an alkyl radical with about 8 to 20 carbon atoms and from 1 to 20% by weight of the detergent composition of a complex aluminum compound soluble in an aqueous solution of said sulfate formed by the reaction of a Water-soluble aluminum salt selected from the group consisting of alum, aluminum sulfate, aluminum acetate, aluminum chloride and aluminum nitrate, and a member selected from the group consisting of tartaric acid, citric acid, malic acid, glycolic acid, lactic acid and the sodium, potassium, ammonium and mixed salts of said acids, said aluminum salt and acid group member reacting in the ratio of about 2.3 mols of salt to one mol of the acid group member in the form of their aqueous solutions, whereupon the pH of the resulting solution is ad justed to from neutral to slightly alkaline, and thereafter the aqueous solution is evaporated to dryness.

9. A detergent composition comprising a water-soluble, alkali metal fatty alcohol sulfonate having an alkyl group derived from normal primary aliphatic alcohols having 10 to 18 carbon atoms and from about 1 to 20% by weight of the detergent composition of a complex aluminum compound soluble in an aqueous solution of said sulfonate formed by the reaction of a Water-soluble aluminum salt selected from the group consisting of alum, aluminum sulfate, aluminum acetate, aluminum chloride and aluminum nitrate, and a member selected from the group consisting of tartaric acid, citric acid, malic acid, glycolic acid, lactic acid and the sodium, potassium, ammonium and mixed salts of said acids, said aluminum salt and acid group member reacting in the ratio of about 2.3 mols of salt to one mol of the acid group member in the form of their aqueous solutions, whereupon the pH of the resulting solution is adjusted to from neutral to slightly alkaline, and thereafter the aqueous solution is evaporated to dryness.

10. A detergent composition comprising a water-soluble alkali metal salt of coconut fatty-alcohol sulfate and from about 1 to 20% by weight of the detergent composition of a complex aluminum compound soluble in an aqueous solution of the detergent composition formed by the reaction of a water-soluble aluminum salt selected from the group consisting of alum, aluminum sulfate, aluminum acetate, aluminum chloride and aluminum nitrate, and a member selected from the group consisting of tartaric acid, citric acid, malic acid, glycolic acid, lactic acid and the sodium, potassium, ammonium and mixed salts of said acids, said aluminum salt and acid group member reacting in the ratio of about 2.3 mols of salt to one mol of the acid group member in the form of their aqueous solutions, whereupon the pH of the resulting solution is adjusted to from neutral to slightly alkaline, and thereafter the aqueous solution is evap orated to dryness.

11. A detergent composition comprising a synthetic capillary active anionic detergent which will not form curd in hard water and from about 1-20% by weight 7 of the detergent composition of acomplex aluminum compound soluble in an aqueous solution of the detergent composition formed by the reaction of a water-soluble aluminum salt selected from the group consisting of alum, aluminum sulfate, aluminum acetate, aluminum chloride and aluminum nitrate, and a member. selected from the group consisting of tartaric acid, citric acid, malic acid, glycolic acid, lactic acid and the sodium, potassium, ammonium and mixed salts of saidacids, said aluminum salt and acid group member reacting in the ratio of about 2.5 mols of salt to one mol of the acid group member in the form of their aqueous solutions, whereupon the pH of the resulting solution is adjusted to from neutral to slightly alkaline, and thereafter the aqueous solution is evaporated to dryness.

References Cited in theifileof this patent" UNITED STATES PATENTS 465,269 Canada e May 23, 1950 

1. A DETERGENT COMPOSITION COMPRISING A SYNTHETIC CAPILLARY ACTIVE ANIONIC DETERGENT WHICH WILL NOT FORM CURD IN HARD WATER AND FROM ABOUT 1-20%, BY WEIGHT OF THE DETERGENT COMPOSITION OF A COMPLEX ALUMINUM COMPOUND SOLUBLE IN AN AQUEOUS SOLUTION OF THE DETERGENT COMPOSITION FORMED BY THE REACTION OF A WATER-SOLUBLE ALUMINUM SALT SELECTED FROM THE GROUP CONSISTING OF ALUM, ALUMINUM SULFATE, ALUMINUM ACETATE, ALUMINUM CHLORIDE AND ALUMINUM NITRATE, AND A MEMBER SELECTED FROM THE GROUP CONSISTING OF TARTARIC ACID, CITRIC ACID, MALIC ACID, GLYCOLIC ACID, LACTIC ACID AND THE SODIUM, POTASSIUM, AMMONIUM AND MIXED SALTS OF SAID ACIDS, SAID ALUMINUM SALT AND ACID GROUP MEMBER REACTING IN THE RATIO OF ABOUT 2.3 MOLS OF SALT TO ONE MOL OF THE ACID GROUP MEMBER IN THE FORM OF THEIR AQUEOUS SOLUTIONS, WHEREUPON THE PH OF THE RESULTING SOLUTION IS ADJUSTED TO FORM NEUTRAL TO SLIGHTLY ALKALINE, AND THEREAFTER THE AQUEOUS SOLUTIO N IS EVAPORATED TO DRYNESS. 